Mordants for bleachable filter layers



United States Patent 3,444,138 MORDANTS FOR BLEACHABLE FILTER LAYERSJack L. R. Williams, Rochester, N.Y.. assignor to Eastman Kodak Company,Rochester, N.Y., a corporation of New Jersey No Drawing. Filed Aug. 16,1965, Ser. No. 480,111 lint. C]. G03c 7/32, 7/28; C09b 65/00 U.S. Cl.260-65 7 Claims ABSTRACT OF THE DISCLOSURE This invention relates tocertain bulky, i.e., relatively high molecular Weight, quaternarynitrogen heterocyclic compounds which function as mordants for use inphotography, and to methods for the preparation of said compounds.

The use of organic dye containing light-filter and lightabsorbing layersin photographic elements is well known, as is the use of mordants whichform substantially insoluble salts or otherwise react with water-solubledyes, to render the dyes non-diffusing. Such dye-mordant lightscreeningsalt may be in a layer overlying a light-sensitive emulsion or overlyingtwo or more light-sensitive emulsions; or it may be in a light-sensitiveemulsion for the purpose of modifying a light record in such emulsion orfor protecting an overlying light-sensitive emulsion or emulsions fromthe action of light of wavelengths absorbed by such light-screeningsubstance, or it may be in a layer not containing a light-sensitivesubstance but arranged between two light-sensitive emulsions; or it maybe in a layer serving as a backing on an element having one or morelight-sensitive emulsions (for example, to reduce halation).

In particular, light-screening substances are often required (a) inovercoatings upon photographic elements to protect the light-sensitiveemulsion or emulsions from the action of light which it is not desiredto record, (-b) in layers arranged between differentially colorsensitized emulsions, e.g., to protect redand green-sensitive emulsionsfrom the action of blue light, and (c) in backings forming the so-calledanti-halation layers on either side of a transparent support carryingthe light-sensitive emulsion or emulsions.

In most cases and especially where the element contains a colorsensitized emulsion or color sensitized emulsions, it is particularlydesirable to employ light-screening substances which do not affect thegeneral sensitivity or the color sensitivity of light-sensitiveemulsions with which they may come into contact. It is also particularlydesirable to employ light-screening substances which do notsubstantially diffuse from the layers or coatings in which they areincorporated, either during the manufacture of the element or on storingit or in photographically processing it. Finally it is generallynecessary to employ light-screening substances which can readily berendered inelfective, i.e., decolorized or destroyed and removed priorto or during or after photographic processing. For many purposes it isparticularly convenient to employ 3,444,138 Patented May 13, 1969light-screening substances which are rendered ineffective by one of thephotographic baths employed in processing the element after exposure,such as a photographic developing bath or fixing bath.

Numerous substances have been proposed as mordants to prepare thedye-mordant salts used as light-screening and light-absorbing materialsfor the purposes indicated above. Among the proposed mordants arerelatively high molecular weight compounds having ionic charges oppositeto those of the particular light-absorbing dye. For example, the dyeemployed might be an acid dye, in which case the mordant would be acationic compound. Typical of such proposed mordants are, for example,derived polymers such as the basic reaction products ofpolyvinylsulfonates and C-aminopyridines as described in D. D. Reynoldset al., US. Patents 2,701,243 and 2,768,078, granted Feb. 1, 1955, andOct. 23, 1956, respectively. While polymeric mordants such asillustrated by the above-mentioned patents have the advantage of bulkymolecules and do function to fix acid dyes in photographic layers,within their particular limitations, they have not been found entirelysatisfactory in many applications primarily because these polymericmordants on alkaline development do not tend to release the dye, i.e.,they still retain their mordanting property and, accordingly, not onlytend to retain some residual dye as evidenced by background stain orcoloration, but more importantly retain, i.e., fix, an appreciableamount of thiosulfate ion in the subsequent hypo processing used toremove unexposed halide. This results in relatively poor quality andstability of the produced image. In view of this, it would be verydesirable to have an effective mordant available that is free from suchdisadvantages.

I have now found that certain bulky or relatively high molecular weightquaternary nitrogen heterocyclic compounds are especially useful asprecipitants and mordants for acid dyes in photographic layers, and thatthese compounds, moreover, satisfactorily overcome the abovementionedshortcomings of heretofore known mordants for this purpose. Thus, ournew class of mordants do not retain any residual dye or deleteriousamounts of thiosulfate ion in the layers after processing, and furtherthe produced images are of very good quality and of outstanding keepingproperties. These novel mordants are soluble in aqueous solutions, forexample, in dilute aqueous solutions of acids such as acetice, butyric,lauric, etc., acids. Furthermore, they have good compatibility withvarious hydrophilic materials such as gelatin and readily formsubstantially non-dilfusible salts with water-soluble acid dyes. Ingeneral, they have a molecular weight of about at least 300, althoughpolymeric materials having a molecular weight of 600 to 50,000, andhigher, have been found to be particularly useful in my invention.

It is, accordingly, an object of the invention to provide a new class ofpolymeric quaternary nitrogen heterocyclic compounds, and salts thereofwith water-soluble acid dyes. Another object is to provide an imbibitionblank containing at least one of the above salts. Another object is toprovide a process for preparing the new class of compounds and salts.Other objects will become apparent from consideration of the descriptionand examples.

The new class of polymeric quaternary nitrogen heterocyclic compounds ofthe invention include those represented by the following generalformula:

(I) o R; x 2.,

R,(o)m 1- i '3111 'r OR:

wherein m represents an integer of from 1 to 2, R, represents a linearpolymeric structure, for example, an addition type polymer such as apolymer of a monoethylenically unsaturated polymerizable compound havingperiodically occurring groups of the structure:

attached to carbon atoms in the polymeric chain of a monoethylenicallyunsaturated polymer (e.g., a polyvinyl ester or alkyl ketone, apolyisopropenyl ester or alkyl ketone), the said chain may also includeunits of vinyl alcohol, unquaternized vinyl ester or vinyl alkyl ketone;R represents the hydrogen atom, a lower alkyl group (e.g., methyl,ethyl, etc.), or a phenyl group; R represents the hydrogen atom, analkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, hexyl,dodecyl, pentadecyl, benzyl, phenethyl, etc.), a hydroxyl, a halogen(e.g., chlorine or bromine), or an aryl group (e.g., phenyl, tolyl,biphenylyl, etc.); X represents an acid anion (e.g., chloride, bromide,iodide, thiocyanate, sulfamate, perchlorate, methyl sulfate, ethylsulfate, p-toluenesulfonate, etc); and Z represents the non-metallicatoms required to complete a nucleus containing a to 6-memberedheterocyclic ring having nitrogen, oxygen, sulfur and selenium as thehetero atoms, typically a thiazole nucleus (e.g., thiazole, 4-methylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole,4,5-diphenylthiazole, 4 (2 thienyl)thiazole, etc.)

a benzothiazole nucleus (e.g., benzothiazole,

4-chlorobenzothiazole, S-chlorobenzothiazole, 6-chlorobenzothiazole,7-chlorobenzothiazole, 4-methylbenzothiazole, S-methylbenzothiazole,tS-methylbenzothiazole, S-bromobenzothiazole, 6-bromobenzothiazole,4-phenylbenzothiazole, 5-phenylbenzothiazole, 4-methoxybenzothiazole,S-methoxybenzothiazole, 6-methoxybenzothiazole, 5-iodobenzothiazole,6-iodobenzothiazole, 4-ethoxybenzothiazole, S-ethoxybenzothiazole,tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole,5,6-dioxymethylenebenzothiazole, S-hydroxybenzothiazole,fi-hydroxybenzothiazole, etc.)

a thianaphtheno- 7',6,4,5-thiazole nucleus, (e.g.,

4'-methoxythianaphtheno- 7',6',4,5-thiazole, etc.

an oxazole (e.g., S-methyloxazole, 4-phenyloxazole,

4,5-diphenyloxazole, 4-ethyloxazole, 4,5-dimethyloxazole,S-phenyloxazole, etc.),

a benzoxazole nucleus (e.g., benzoxazole,

Schlorobenzoxazole, S-methylbenzoxazole, S-phenylbenzoxazole,-methylbenzoxazole, 5,6-dirnethylbenzoxazole, 4,6-dimethylbenzoxazole,S-methoxybenzoxazole, S-ethoxybenzoxazole, 6-chlorobenzoxazole,S-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc.)

a naphthoxazole nucleus (e.g., u-naphthoxazole, fl,,8-naphthoxazole,,B-naphthoxazole, etc.),

a selenazole nucleus (e.g., 4-methylselenazole,

4-phenylselenazole, etc.),

a benzoselenazole nucleus (e.g., benzoselenazole,

S-chloroselenazole, S-methoxybenzoselenazole, S-hydroxybenzoselenazole,tetrahydrobenzoselenazole, etc.

a naphthoselenazole nucleus (e. g., u-naphthoselenazole,fiJi-naphthoselenazole, fl-naphthoselenazole, etc.

a thiazoline nucleus (e.g., thiazoline,

4-methylthiazoline, etc.)

a quinoline nucleus (e.g., quinoline,

3-methylquinoline, S-methylquinoline, 7-methylquinoline,8-methylquinoline, 6-chloroquinoline, S-chloroquinoline,6-methoxyquinoline, 6-ethoxyquinoline, 6-hydroxyquinoline,8-hydroxyquinoline, etc.),

an isoquinoline nucelus (e.g., isoquinoline,

4 3-methylisoquinoline, S-methylisoquinoline, 6-chloroisoquinoline,6-methoxyisoquinoline, 8-hydroxyisoquinoline, etc.

a 3,3-dialkylindolenine nucleus (e.g.,

3,3-dimethylindolenine, 3,3,S-trimethylindolenine, 3 ,3,7-trimethylindolenine, etc.

a pyridine nucleus (e.g., pyridine, Z-methylpyridine,

2-benzylpyridine, 3-chloropyridine, 3-hydroxypyridine,2-rnethyl-5-ethylpyridine, 2,5-dibutylpyridine,3-diphenylmethylpyridine, 4-diphenylmethylpyridine,hydroxydiphenylmethylpyridine, etc.

an imidazole nucleus (e.g., imidazole, l-alkyl imidazole,

1-alkyl-4-phenylimidazole, 1-alkyl-4,5-dimethylimidazole, etc.

a benzimidazole nucleus (e.g., benzimidazole,

l-alkylbenzimidazole, 1-aryl-5,6-dichlorobenzimidazole, etc.),

a naphthimidazole nucleus (e.g., 1-alkyl-a-naphthimidazole,l-aryl-fl-naphthimidazole, 1-alkyl-5-rnethoxy-u-naphthimidazole, etc.

a 1,2,4-thiadiazole nucleus,

a l or 4 alkyl-1,2,4-triazole nucleus (e.g.,

1-methyl-1,2,4-triazole, 1-butyl-1,2,4-triazole, 4-ethyl-1,2,4-triazole,etc.)

a tetrazole nucleus (e.g., tetrazole,

S-methyl-1,2,3,4-tetrazole,

S-phenyl-l ,2,3,4-tetraz0le, etc.

and the like nuclei.

More particularly the new class of quaternary nitrogen heterocyclicpolymers of the invention include derived resinous copolymers consistingessentially of not less than 25% by weight of polymerized units of thegeneral structure:

the remainder of the polymer molecule may be polymerized units of thestructures:

and/ or when m is the integer 2.

In accordance with the invention, I prepare the derived resinouscopolymer coming under above Formula II by reacting a resinous additionpolymer of a monoethylenically unsaturated polymerizable compound havingthe general formula:

(IV) 0 R;

with a heterocyclic tertiary amine having the general formula:

N CR3 prepared, for example, by polymerizing monomeric vinylchloromethyl ketone (Catch et al., J. Chem. Soc., 1948, p. 278) in asolvent such as dioxane at 60 C. in the presence of a polymerizationcatalyst, e.g., azo-bis-isobutyronitrile. The proportions of theheterocyclic tertiary amine of Formula V above can vary widely, butpreferably it is employed in the reaction in excess of thestoichiometrically calculated quantity, for example, from about 1.2 to5, or more equivalent moles. Advantageously, the reaction is carried outin an inert reaction medium which is a solvent for the starting polymersuch as, for example, in acetone, dimethyl sulfoxide,N,N-dimethylformamide, 'y-butyrolactone etc. The reaction mixture isallowed to stand for several days or more at room temperatures or heatedfor several hours. The quaternary salt product which forms is isolatedby precipitation into a nonsolvent for the salt product, or in the casewhere the salt product forms as a precipitate in the reaction mixture,the supernatant liquor can be simply decanted. The quaternary saltproduct can then be further purified by washing with a non-solvent anddried preferably under vacuum. The quaternary salt products consistingfrom about 25-100% by weight of quaternized units and from 75-0%, byweight of unquaternized residual units have been found to be especiallyefilcacious mordants in photographic layers and are preferred.

The photographic elements prepared with the abovedescribed polymeric andnon-polymeric mordants of the invention comprise a support materialhaving thereon at least one hydrophilic colloid layer containing amordant of the invention, which layer may also contain a lightsensitivesilver halide. However, the preferred light-sensitive photographicelements comprise a support having thereon at least one hydrophiliccolloid layer containing a mordant of the invention and at least onelight-sensitive silver halide emulsion layer. The mordant containinglight-screening and antihalation layers are customarily prepared bycoating on the sup ort or photographic element by methods well known inthe art, a water solution comprising at least one mordant of theinvention, an acid dye, a water permeable hydrophilic colloid binder anda coating aid such as saponin. For most purposes, it is also desirableto add agents to harden the colloidal binder material so that thelight-screening layer will remain intact in the photographic elementduring and following the processing operations. The pH of the coatingsolution is adjusted when necessary to a level that is compatible withthe light-sensitive emulsion layer by the usual methods. The proportionsof mordant, dye, colloidal binder, hardener and coating aid may bevaried over wide ranges and will depend upon the specific requirementsof the photographic element being produced. The methods used todetermine the optimum compositions are well known in the art and requireno further elucidation here. Suitable support materials include any ofthose used in photography such as cellulose acetate, cellulosepropionate, cellulose acetate-butyrate, cellulose nitrate, syntheticresins such as nylon, polyesters, polystyrene, polypropylene, etc.,paper, and the like.

Suitable hydrophilic colloid materials that can be used in the mordantcontaining compositions and layers, and photographic elements, of theinvention include gelatin, albumin, collodion, gum arabic, agar-agar,cellulose derivatives such as alkyl esters or carboxylated cellulose,hydroxy ethyl cellulose, carboxy methyl hydroxy ethyl cellulose,synthetic resins, such as the amphoteric copolymers described by Clavieret al. in U.S. Patent 2,949,442, issued Aug. 16, 1960, polyvinylalcohol, polyvinyl pyrrolidone, and others Well known in the art. Theabove-mentioned amphoteric copolymers are made by polymerizing themonomer having the formula:

CH2=CR' COOH wherein R represents an atom of hydrogen or a methyl group,and a salt of a compound having the general formula:

wherein R has the above-mentioned meaning, such as an alkylamine salt.These monomers can further be polymerized with a third unsaturatedmonomer in an amount up to about 20 percent, and preferably from 5-15percent, of the total weight of monomer used, such as an ethylenemonomer that is copolymerizable with the two principal monomers. Thethird monomer may contain either a basic group or an acid group and may,for example, be vinyl acetate, vinyl chloride, acrylonitrile,methacrylonitrile, styrene, acrylates, methacrylates, acrylamide,methacrylamide, etc. Examples of these polymeric gelatin substitutes arecopolymers of allylamine and methacrylic acid; copolymers of allylamine,acrylic acid and acrylamide; hydrolyzed copolymers of allylamine,methacrylic acid and vinyl acetate; the copolymers of allylamine,acrylic acid and styrene; the copolymers of allylamine, methacrylic acidand acrylonitrile; etc.

The dyes that can be effectively mordanted in accordance with myinvention include any filter dye that has one or more acidic groupsubstituents such as sulfo or carboxyl groups, for example, the oxonoldyes described and claimed in copending application of Joseph Bailey,Ser. No. 98,709, filed Mar. 27, 1961, having the formula:

and more particularly the dyes of the formula:

0 II C wherein Z represents the nonmetallic atoms necessary to completea 1-carboxyalkyl-3-hydrocarbon substitutedhexahydro-2,4,6,-trioxo*5pyrimidine nucleus, 12 in each case is aninteger of from 1 to 3, each R represents a carboxyalkyl group in whichthe carboxy substituent is attached to an alkyl group having from 1 to 2carbon atoms, R is an alkyl group of from 1 to 8 carbon atoms or an arylgroup such as phenyl or an alkyl or alkoxy substituted phenyl group, andX is hydrogen or an alkyl group of from 1 to 4 carbon atoms, such thatno more than one X is an alkyl group. Other suitable acid dyes includethe benzoxazolepyrazolone merocyanine dyes described in copendingapplication of Jones et al. U.S. Ser. No. 167,666, filed J an. 22, 1962having the formula:

wherein R represents an alkyl group such as methyl, ethyl, propyl,isopropyl, butyl, isobutyl, tertiary butyl, etc., or a carboxyalkylgroup, such as carboxymethyl, carboxyethyl, carboxypropyl, etc., or asulfoalkyl group, such as sulfoethyl, sulfopropyl, sulfobutyl, etc.; Zrepresents the nonmetallic atoms necessary to complete a heterocylicnucleus of the benzoxazole series (including benzoxazole and benzoxazolesubstituted with substitutions such as methyl, ethyl, phenyl, methoxy,ethoxy, chlorine, bromine, etc.) or a nucleus of the benzoxazoles serieswhich has a sulfo-substituent on the benzene ring as well as one or moreof the above-mentioned simple substituents, such that when R representsan alkyl group, Z represents the sulfo-substituted benzoxazole nucleusand when R represents a carboxyalkyl group or a sulfoalkyl group, Zrepresents the nonmetallic atoms necessary to complete a benzoxazolenucleus; Q represents the nonmetallic atoms necessary to complete aheterocyclic nucleus of the sulfophenyl pyrazolinone series and n is aninteger from 1 to 3. However, the invention is not limited to just thosedyes coming within the general formulas of the above-mentioned copendingapplications, since as previously set forth any filter dye containingone or more sulfo or carboxyl groups can be employed. For example, theyellow dyes mentioned in Mader et al. US. Patent 3,016,306, issued Jan.9, 1962, columns and 6.

Typical light-filtering dyes include, for example, bis(lbutyl 3-carboxymethylhexahydro-2,4,6-trioxo-5-pyrimidine)-pentamethineoxonol,bis 1-carboxymethyl-3-cyclohexylhexahydro 2,4,6trioxo-S-pyrimidine)pentamethineoxonol, bis(lbutyl-3-carboxymethylhexahydro-2,4,6- trioxo 5pyrimidine)trimethineoxonol, bis(l-carboxymethylhexahydro 3 octyl2,4,6-trioxo-5-pyrimidine) meth'ineoxonol, 4 [(3ethyl-2(3H)-benzoxazolylidine) ethylidene] 3methylI-(p-sulfophenyl)-2-pyrazolin-5- one monosulfonated,4-[4-(3-ethyl-2 (3H)-benzoxazolylidene) 2butenylidene]-3-methyl-'1-(p-sulfophenyl)-2- pyrazolin 5-onemonosulfonated, 4-[(3-;i-carboxyethyl- 2(3H)benzoxazolylidene)ethylidene] 3-methyl-1-(psulfophenyl)2-pyrazolin-5-one, 4-[4-(3-p-carboxyethyl- 2(3H)benzoxazolylidene)-2-butenylidene]-3-methyl-1-(p-sulfophenyl)-2-pyrazolin-5-one, bis( 1-butyl-3-carboxymethyl-S-barbituric acid)trimethine oxonol, bis(l-butyl-3-carboxymethyl-5-barbituric acid) pentamethineoxonol, bis[3 methyll-(p-sulfophenyl)-2-py-razolin-5-one-(4)] methineoxonol, 'bis[3me'thyl-l-(p-sul fophenyl)-2-pyrazolin 5 one (4)]trimethineoxonol,bis[3-methyl-1-(psulfophenyl) 2 pyrazolin 5 one (4)] pentamethineoxonol,bis[3 methyl l-(p-sulfophenyl)-5-pyrazo1one- (4)]pentamethineoxonol, andtypical ultraviolet absorbing dyes include the 2,5-bis(substitutedsulfophenyl)thiazolo[5,4-d]thiazole disodium salts of Sawdey U.S. Ser.183,417, filed Mar. 29, 1962, such as2,5-bis(o-methoxyxsulfophenyl)thiazolo[5,4-d]thiazole disodium salt,2,5- bis(o hexyloxy-x-sulfophenyl)thiazolo[5,4-d] thiazole disodiumsalt, 2,5 -bis(o-decyloxy-x-sulfophenyl)thiazolo [5,4-d]thiazoledisodium salt, 2,5-bis(o-methyl-x-sulfophenyl)thiazolo[5,4-d]thiazoledisodium salt, 2,5-bis(5- butyl 2 methylx-sulfophenyl)thiazolo[5,4-d]thiazole disodium salt, 2,5bis(m-methyl-x-sulfophenyl)thiazolo [5,4-d]thiazole disodium salt,2,5-bis(p-propyl-x-sulfophenyl)thiazolo[5,4-d]thiazole disodium salt,etc.; the ultraviolet absorbing dyes of Sawdey US. Patent 2,739,- 888,issued Mar. 27, 1956, such as 3-phenyl-2-phenylimino-5-o-sulfobenZal-4thiazolidone sodium salt, 5 (4- methoxy 3sulfobenzal)-3-phenyl-2-phenylimino-4-thiazolidone (sodium salt),3-phenyl-2-phenylimino-5-[3-(3- sulfobenzamido)benzal1-4-thiazolidone(sodium salt), 3- benzyl 2 phenylimino 5-o-sulfobenzal-4-thiazolidone(sodium salt), 5 2,4-dicarboxymethoxybenzal -3phenyl-2-phenylimino-4-thiazolidone sodium salt, etc., tartrazine, and the likefilter dyes.

Hardening materials that may be used to advantage include such hardeningagents as formaldehyde; a halogen-substituted aliphatic acid such asmucobromic acid as described in White U.S. Patent 2,080,019, issued May11, 1937; a compound having a plurality of acid anhydride groups such as7,8-diphenylbicyclo (2,2,2)-7- octene-2,3,5,6-tetra-carboxylicdianhydride, or a dicarboxylic or a disulfonic acid chlorine such asterephthaloyl chloride or naphthalene-1,5-disulfonyl chloride asdescribed in Allen and Carroll US. Patents 2,725,294 and 2,725,295, bothissued Nov. 29, 1955; a cyclic 1,2-diketone such as-cyclopentane-1,2-dione as described in Allen and Byers US. Patent2,725,305, issued Nov. 29, 1955; a bisester of methane-sulfonic acidsuch as l,2-di(methanesulfonoxy)ethane as described in Allen and LaaksoUS. Patent 2,726,162, issued Dec. 6, 1955;1,3-dihydroxymethylbenzimidazol-Z-one as described in July, Knott andPollak, US. Patent 2,732,316, issued Jan. 24, 1956; a dialdehyde or asodium bisulfite derivative thereof, the aldehyde groups of which areseparated by 2-3 carbon atoms, such as ,B-methyl glutaraldehydebis-sodium bisulfite as described in Allen and Burness, Canadian PatentNo. 588,451, issued Dec. 8, 1959; a bis-aziridine carboxamide such astrimethylene bis(l-aziridine carboxamide) as described in Allen andWester US. "Patent 2,950,197, issued Aug. 23, 1960; or2,3-dihydroxydioxane as described in Jeffreys US. Patent 2,870,013,issued Jan. 20, 1959.

The photographic element utilizing my light-screening layers havelight-sensitive emulsion layers containing silver chloride, silverbromide, silver chlorobromide, silver iodide, silver bromoiodide, silverchlorobromoiodide, etc., as the light-sensitive material. Anylightsensitive silver halide emulsion layers may be used in thesephotographic elements. The silver halide emulsion may be sensitized byany of the sensitizers commonly used to produce the desiredsensitometric characteristics.

My invention is further illustrated by the following examples describingthe preparation of preferred mordants and the use thereof inphotographic elements.

EXAMPLE 1 Poly(vinyl pyridiniumacetate chloride) (A) 20 g. (approx. 0.17mol.) of polyvinyl chloroacetate was dissolved in 200 ml. of acetone.Then 40 ml. (approx. 0.47 mol.) of pyridine was added and the mixtureallowed to stand overnight at room temperature. Soft material hadprecipitated. The supernatant liquid was decanted. The residue wasdissolved in methanol, precipitated in ether, washed, and vacuum dried.It was then redissolved in methanol and reprecipitated in ether, washed,and vacuum dried. Analysis of this product showed that it contained 2.8%by weight of nitrogen as compared with calculated theory ofapproximately 7% by weight of nitrogen for pure poly(vinyl pyridiniumacetate) chloride. Accordingly, this derived polymer consistedessentially of about 40% by weight of recurring (vinyl pyridiniumacetate) chloride units of the structure:

and the remainder of the polymer to make of recurring units of unreactedvinyl chloroacetate.

(B) A solution of 6.0 g. (approx. 0.5 mol.) of polyvinyl chloroacetatein 100 ml. of dimethyl sulfoxide was treated with 10 g. (approx. 0.13mol.) of pyridine. The mixture was allowed to stand 5 days. The polymerwas then precipitated in acetone, washed and vacuum dried. It wasredissolved in methanol and reprecipitated in ether, washed and vacuumdried. The yield of product was 9 g. Analysis of this product showedthat the derived polymer consisted essentially of about 77% by weight ofrecurring units of vinyl pyridinium acetate chloride and 23% by weightof recurring units of unreacted vinyl chloroacetate.

(C) Substantially 100% poly(vinyl pyridiniumacetate chloride) wasobtained by using pyridine as the solvent and heating to 70 C. for about2 hours.

EXAMPLE 2 A solution of 60.0 g. (approx. 0.57 mol.) of poly (vinylchlorornethyl ketone) in 600 ml. of N,N-dimethylformamide was treatedwith 1.25 ml. (approx. 11.58 mol.) of pyridine. The mixture was allowedto stand for 6 days. A soft precipitate formed. The supernatant liquorgave no precipitate in ether and discarded. The residue was dissolved in1510 ml. of methanol, precipitated in acetone, washed and vacuum dried.It was re-dissolved in methanol, reprecipitated in acetone and dried.The yield was 55 g. Analysis of this product showed that it contained3.8%

by weight of nitrogen as compared with calculated theory ofapproximately 7.6% by weight of nitrogen. Accordingly, this derivedpolymer consisted essentially of about 49.8% by weight of recurring(vinyl pyridinium methyl ketone) chloride units of the structure:

and the remainder of the polymer molecule to make 100% of recurringunits of unreacted vinyl chloromethyl ketone.

The use of my novel and valuable polymers as mordants in filter layerswill be illustrated with the following examples.

EXAMPLE 3 To 1.0 cc. of 1 photographic gelatin melted at 40 C. was added30 mg. of poly(vinyl pyridinium acetate) chloride dissolved in 10 cc. ofwater. The pH of the solution was adjusted to 4.5-5.0 with glacialacetic acid. To this was added 10 rngs. ofbis[3-methyl-l-p-sulfophenyl-5- pyrazolone(4) ]pentamethene-oxonoldissolved in water with vigorous stirring. The pH of the melt was thenreadjusted to 60:0.1 with 2.5 N sodium hydroxide solution, a coating aidadded, the total volume adjusted to 32 cc. with distilled water and themelt coated on a film support and dried.

No signs of dye bleeding out of the gel layer were noted when a portionof the dried coating was immersed in stagnant distilled water at 75 F.for 2 minutes, nor after a second 2-minute immersion in the water.

Another portion of the coating was treated in a conventional alkalinesilver halide developer solution containing hydroquinone andp-methylaminophenol sulfate as the developing agents. The mordanted dyewas completely bleached by this treatment. Following treatment in thedeveloper, the coating was treated in a conventional sodium thiosulfatefixing bath and then Washed. No residual sodium thiosulfate was detectedin the coating by the Ross-Crabtree method.

Similar results were obtained when coatings were made substituting thecorresponding trimethineoxonol dye and the corresponding monomethineoxonol dye for the pentamethine-oxonol dye. Coatings were made in whicheach of the above dyes were mordanted with poly(vinyl pyridinium methylketone) chloride instead of poly(vinyl pyridinium acetate) chloride.Each of these coatings showed no bleeding of dyes on immersion in water,but complete dye bleaching in the developer solution. No residual sodiumthiosulfate was detected by the Ross- Crabtree method in the developed,fixed and washed coatmgs.

EXAMPLE 4 This example shows the use of the :derived polymers of theinvention as on ultraviolet absorbing overcoating layer overlight-sensitive gelatino-silver halide emulsion layers, for example,over the emulsion layers of a multilayer color element of the typedescribed in Mannes et al., US. Patent 2,252,718, issued Aug. 1 9, 1941.

A gelatin-mordant composition was prepared by mixing 200 g. of a 10%aqueous gelatin solution at 40 C. and 200 g. of a 15% aqueous solutionof the polymeric mordant prepared according to Example .1(A) at 40 C.The clear solution obtained was then chilled, noodled, and washed withcold water in the normal manner for 6 hours, drained, remelted at 0 C.and (weighed.

A coating melt was then prepared as follows employing the abovegelatin-mordant composition.

Coating melt Gelatin containing 7.7 g. of Example 1 polymer Sulfurdioxide hydroquinone clathrate g 0.32 Adjust solution pH=6.07 $0.07 withlauric acid Adjust solution pH=6.2 Distilled water (to make total melt)g 383 The sulfur dioxide hydroquinone clathrate is described by H. M.Powell, J. Chem. Soc. (1948), pages 61-73; CA. 42, 5293 (1948). Thismelt was then coated over the emulsion layers of the above rnentionedmultilayer color element at 6 g./sq. ft. (containing 1.33% gelatin) togive a coating comprising 120 mg./sq. ft. of the polymeric mordant ofExample .1 and 40 mg./sq. ft. of the filter dye in mg./sq. ft. of gel.On sectioning of the coated element and in photographs made therewith,no bleeding of the dye was noted. Allcaline processing conditions leftno dye residue and yet no stain increase was noted, implying betaineformation of the mordant with internal charge compensation. Also, nodetectable thiosulfate was retained in the fixed element.

My alkali-release polymeric mordants are also used to advantage inmordanting light-filtering dyes, such as a blue-light absorbing dyehaving one or more acid substitutents, in a filtering layer between thetop blue-sensitive layer and over the green-sensitive and thered-sensitive layers of a multilayer color photographic element of thetype described in Mannes et al. US. Patent 2,252,7 1 8, referred topreviously. Alternatively, appropriate dyes of other colors can be usedto advantage in mordanted filter layers between the green-sensitive andred-sensitive layers, or one or more appropriate dyes can be mord antedin an antihalation layer either between the light-sensitive layers andthe support or on the side of the support away from the light-sensitivelayers.

Examples 5 through 8 illustrate the use of the derived polymericmordants of the invention in antihalation layers, and further illustratethe improvement obtained therewith in regard to hypo retention in theprocessed elements, as compared with an element prepared [with a knownmordanting polymer and a non-mordanted control element.

In each of the following examples, the coating melts were prepared, ingeneral, by the procedure described in above Example 4. The meltcompositions, with the exception of the control example, were coated onan ordinary cellulose acetate film support and over this melt layer wascoated in each case a fine-grained silver chlorobromide gelatin emulsionlayer. For convenience, the filter dyes employed are listed as follows:

Dye A.--4-[(3-ethyl 2(3H) benzoxazolylidene)ethylidene] 3 methyl-l-psulfophenyl-2-pyrazolin-5-one, monosulfonated Dye B.Bis(1butyl-3-carboxymethyl-5-barbituric acid) tri-methineoxonol Dye C.4- [4-3-ethyl-2( 3H -benzoxazolylidene -2-butenylidene]3-methyl-1-p-sulfophenyl-Z-pyrazolin-5-one, monosulfonated DyeD.Bis(1-butyl-3-carboxymethyl-S-barbituric acid) pentamethineoxonol DyeE.--Bis[3 methyl-l-(p-sulfophenyl)-2-pyrazolin-5- one (4) -methineoxonol11 Dye F.-Bis[3 methyl-l-(p-sulfophenyl)-2-pyrazolin-5- one- (4)]-trimethineoxonol Dye G.Bis[3 methyl-l-(p-sulfophenyl)-2-pyrazolin-5-one 4) ]-pentamethineoxonol EXAMPLE 5 A control film element was coatedhaving no antihalation undercoat.

EXAMPLE 6 A film element was coated having an antihalation undercoatcomprising gelatin+poly(a-methylallyl-N-guanidyl-ketimine, glycolic acidsalt) prepared in accordance with Minsk U.S. Patent 2,882,156, issuedApr. 14, 1959, as the mordant polymer (28 mg./ft. Dye A (2.4 mg./ ft.Dye B (1.6 mg./ft. Dye C (2.9 mg./ft and Dye D (2.5 mg./ft

EXAMPLE 7 A film element was coated having an antihalation undercoatcomprising gelatin and the polymeric mordant of Example 1(A) (45 mg./ft.Dye A (2.4 mg./ft Dye B (1.6 mg./ft. Dye C (2.9 mg./ft. and Dye D (2.5mg./ft.

EXAMPLE 8 A film element was coated having an antihalation undercoatcomprising gelatin and the polymeric mordant of Example 1(A) (45 mg./ft.Dye E (5 mg./ft. Dye F (5 rug/ft?) and Dye G (5 mg./ft.

The film coatings of above Examples 5, 6, 7 and 8 were exposed on anintensity scale sensitometer, developed for 2 in a conventional alkalinedeveloper solution using hydroquinone and p-methylaminophenol sulfate asthe developing agents at 80 F., fixed in a conventional sodiumthiosulfate fixing bath that was substantially neutral, washed anddried. The processed strips were analyzed for residual hypo. Thefollowing results were obtained:

Hypo

Relative Retention Example Speed 7 Fog (mg/in!) It will be noted fromthe above-tabulated results that the hypo retention by the film elementsprepared with a polymeric mordant of the invention (Examples 7 and 8)was practically negligible in amount ranging only from 0.002 to 0.009mg./iu. whereas the film element (Example 6) prepared withpoly[u-methyallyl-N-guanidylketimine, glycolic acid salt] showed a hyporetention many fold greater than 0.032 mg./in.

Similar results are obtained by substituting the following mordants forpoly(vinyl pyridiniumacetate chloride) in the preceding examples.

The above mordants are prepared according to the methods of theinvention described in Examples 1 and 2 by reacting polyvinylchloroacetate or poly(vinyl chloromethyl ketone) with the appropriateheterocyclic amine.

The use of my polymeric mordants in light-screening layers overlight-sensitive silver halide emulsion layers,

and in antihalation undercoat layers, to produce improved photographicelements has been illustrated in the preceding examples. However, itwill be apparent that the mordants of the invention can also beadvantageously used in light-screening layers between two or more colorsensitized silver halide emulsion layers, or in antihalation backinglayers, or incorporated directly in light-sensitive silver halideemulsion layers, or they can be used to prepare imbibition dye transferblanks of improved properties.

The invention has been described in detail with particular reference topreferred embodiments thereof but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention as described hereinabove and as defined in the appendedclaims.

I claim: 1. A compound selected from those having the formula:

0 R: I Z Ri(0)mi J H-Il E) R3 wherein m, R R Z and X are as definedpreviously.

2. A compound of claim 1 in which Z represents the atoms required tocomplete a nucleus selected from the class consisting of a thiazolenucleus, a benzothiazole nucleus, a naphthothiazole nucleus, athianaphtheno-7',6,4,5- thiazole nucleus, an oxazole nucleus, abenzoxazole nucleus, a naphthoxazole nucleus, a selenazole nucleus, abenzoselenazole nucleus, a naphthoselenazole nucleus, a thiazolinenucleus, a quinoline nucleus, an isoquinoline nucleus, a pyridinenucleus, an imidazole nucleus, 21 benzimidazole nucleus, anapththimidazole nucleus, a 3,3-dialkylindolenine nucleus, a1,2,4-thiadiazole nucleus, a 1,2,4-triazole nucleus, and a tetrazolenucleus.

3. A resinous linear polymer derived from a monoethylenicallyunsaturated polymerizable compound and having periodically occurringgroups attached to carbon atoms of the polymer chain of the structure:

wherein m represents an integer of from 1 to 2, R represents a memberselected from the class consisting of the hydrogen atom, a lower alkylgroup and a phenyl group, R represents a member selected from the classconsisting of the hydrogen atom, an alkyl group and an aryl group, Xrepresents an acid anion, and Z represents the nonmetallic atomsrequired to complete a heterocyclic nucleus selected from the classconsisting of a thiazole nucleus, a benzothiazole nucleus, anaphthothiazole nucleus, a thianaphtheno-7',6,4,5-thiazole nucleus, anoxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, aselenazole nucleus, a benzoselenazole nucleus, a naphthoselenazolenucleus, 21 thiazoline nucleus, a quinoline nucleus, an isoquinolinenucleus, a pyridine nucleus, an imidazole nucleus, a benzimidazolenucleus, a naphthimidazole nucleus, a 3,3-dialkylindolenine nucleus, a1,2,4-thiadiazole nucleus, at 1,2,4-triazole nucleus, and a tetrazolenucleus.

4. A resinous copolymer which functions as an alkalirelease mordant foracid dyes consisting essentially of from about 25100% by weight ofrecurring polymerized units of the structure:

and from 750% by weight of recurring polymerized units selected from theclass consisting of those having the formula:

wherein m in each occurrence represents the same integer of from 1 to 2,R in each occurrence represents the same member selected from the classconsisting of the hydrogen atom, a lower alkyl group and a phenyl group,X in each occurrence represents the same acid anion, R represents amember selected from the class consisting of the hydrogen atom, an alkylgroup and an aryl group, and Z represents the non-metallic atomsrequired to complete a heterocyclic nucleus selected from the classconsisting of a thiazole nucleus, a benzothiazole nucleus, atnaphthothiazole nucleus, a thianaphthen-7',6,4,S-thiazole nucleus, anoxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, aselenazole nucleus, a benzoselenazole nucleus, a

naphthoselenazole nucleus, a thiazoline nucleus, a quinoline nucleus, anisoquinoline nucleus, a pyridine nucleus, an imidazole nucleus, abenzimidazole nucleus, a naphthimidazole nucleus, a3,3-dialkylindolenine nucleus, a 1,2,4- thiadiazole nucleus, a1,2,4-triazole nucleus, and a tetrazole nucleus.

5. A resinous copolymer which functions as a mordant for acid dyesconsisting essentially of from about 25- 100% by weight vinylpyridiniumacetate chloride units and from about 0% by weight of vinylchloroacetate units.

6. A resinous copolymer which functions as a mordant for acid dyesconsisting essentially of from about 25100% by weight of vinylpyridiniummethyl ketone chloride units and from about 750% by weight ofvinyl chloromethyl ketone units.

7. A non-sensitive element comprising a support material having thereona hydrophilic colloid layer containing at least one compound of claim 1.

References Cited UNITED STATES PATENTS 5/1952 Cofiman 260-63 US. Cl.X.R.

